JP2877895B2 - Positive photosensitive resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a heat-resistant positive photosensitive resin composition useful for forming a protective layer and an insulating layer in the field of electronics.

[Prior Art] Generally, positive resists are produced by adding O-quinonediazide or naphthoquinonediazide as a photosensitizer to an alkali-soluble novolak resin. However, this positive-type novolak resin has low heat resistance and is not suitable for a semiconductor processing process at a high temperature. Therefore, in recent years, a heat-resistant photoresist having a stable pattern shape at high temperatures has been developed. As an example,
There is a heat-resistant positive resist in which a photosensitive diazoquinone is added to an oligomer or polymer precursor of polybenzoxazole described in JP-A-56-27140.
However, since this resist has too high solubility, there is a drawback that the film is greatly reduced in the developing step and the processing width is small. In addition, similar to a general novolak-based positive resist, the adhesion to a silicon oxide film or the like is poor, and the pattern is peeled off during development. Therefore, the surface of the wafer is exposed to a silylamine derivative such as hexamethyldisilazane or chloromethylsilane. Must be pre-processed.

[Problems to be Solved by the Invention] The present invention provides a positive photosensitive resin composition comprising a polybenzoxazole precursor having a wide processing width in a developing step and having high adhesion to a silicon oxide film. To be.

[Means for Solving the Problems] The present invention provides (1) the following formulas [I], [II], [III],
Monomers (A), (B), and (B) having a group represented by [IV]
(C), (D) (Wherein, W: divalent aromatic group) (Wherein, X: tetravalent aromatic group 1: 0-2 m: 1-2 21 + m = 2 (Wherein, Y is a divalent aromatic group) (D) -NH-Z-NH -... [IV] (where Z is a divalent aromatic group or an aliphatic group) is polymerized at the following ratio. (A) 2 to 50 mol%, (B) 2 to 50 mol%, (C) 0 to 48 mol%, (D) 0 to 48 mol% (however, (D) does not include 0 mol%) A positive photosensitive resin composition comprising a polybenzoxazole precursor having a degree of polymerization of 2 to 500.

(2) The ratio of the total number of m groups in the precursor is The positive photosensitive resin composition according to claim 1, wherein the composition is:

(3) a siloxane compound group in which the Z group in the precursor is represented by the following formula [V] (Wherein, R ₁ , R ₂ : divalent aliphatic group, aromatic group R ₃ , R ₄ , R ₅ , R ₆ : monovalent aliphatic group, aromatic group k: 1 to 100) 3. The positive photosensitive resin composition according to claim 1, wherein the monomer content is 2 to 20 mol%.

[Action] W in the group represented by the formula [I] of the present invention or formula [II]
Y in the group represented by I] is two aromatic groups, for example, _{(Wherein, A: -CH 2 -, -} O -, - S -, - SO 2 -, - CO
-, - NHCO -, - C (CF 3) -) but the like, not limited to this and W
And Y may be the same or different. X in the group represented by the formula [II] of the present invention is a tetravalent aromatic group, for example, _{(Wherein, A: -CH 2 -, -} O -, - S -, - SO 2 -, - CO
-, - NHCO -, - C (CF 3) -) but the like, but is not limited thereto. Z in the group represented by the formula [IV] of the present invention represents a divalent aromatic group or an aliphatic group, and as a raw material monomer containing the group, for example, m-phenylene-diamine, p-phenylene- Diamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 1-isopropyl-2,4-phenylene-diamine,
Bis (trifluoromethyl) phenylenediamine, m-
Xylylene-diamine, p-xylylene-diamine, methylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, 3-methoxy-hexamethylenediamine, heptamethylenediamine, 2,5- Dimethyl-heptamethylenediamine, 3-methylheptamethylenediamine, 4,4-dimethyl-heptamethylenediamine, octamethylenediamine, nonamethylenediamine,
5-methyl-nonamethylenediamine, 2,5-dimethyl-
Nonamethylenediamine, decamethylenediamine, ethylenediamine, propylenediamine, 2,2-dimethyl-propylenediamine, 1,10-diamino-1,10-dimethyldecane, 2,11-diamino-dodecane, 1,12-diamino-octadecane 2,12-diamino-octadecane, 2,17-diamino-icosane, 3,3'-diamino-diphenylmethane, 4,4-diamino-diphenylmethane, 3,3-dimethyl-4,4'-diamino-diphenylmethane, bis (P-
Amino-cyclohexyl) methane, 3,3'-diamino-
Diphenylethane, 4,4'-diamino-diphenylethane, 4,4'-diamino-diphenyl ether, bis (p
-Β-amino-t-butylphenyl) ether, 3,3 '
-Dimethyl-4,4'-diamino-diphenyl ether,
3,3'-diamino-diphenylpropane, 4,4'-diamino-diphenylpropane, 2,2'-bis (p-aminophenyl) propane, 2,2'-bis (aminophenyl) hexafluoropropane, 2'-bis [4- (p-aminophenoxy) phenyl] propane, 2,2'-bis [(aminophenoxy) phenyl] hexafluoropropane, bis {[(trifluoromethyl) aminophenoxy] phenyl} hexafluoropropane , 2,5-diamino-m-xylene, 2,5-diamino-p-xylene, 2,6
-Diamino-pyridine, 2,5-diamino-pyridine, 2,6
-Diamino-4-trifluoromethylpyridine, 2,5-
Diamino-1,3,4-oxadiazole, 1,4-diamino-
Cyclohexane, piperazine, 4,4'-methylene-dianiline, 4,4'-methylene-bis (o-chloroaniline), 4,4'-methylene-bis (3-methylaniline), 4,4'-methylene- Bis (2-ethylaniline), 4,4'-methylene-bis (2-methoxyaniline), 4,4'-methylene-bis (2-methylaniline), 4,4'-oxy-dianiline, 4,4 '-Oxy-bis (2-methoxyaniline), 4,4'-oxy-bis (2-chloroaniline), 4,4'-thio-dianiline,
4,4'-thio-bis (2-methylaniline), 4,4'-thio-bis (2-methoxyaniline), 4,4'-thio-bis (2-chloroaniline), 3,3'- Sulfonyl-dianiline, 4,4'-sulfonyl-dianiline, 4,4'-sulfonyl-bis (2-methylaniline), 4,4'-sulfonyl-bis (2-ethoxyaniline), 4,4'-sulfonyl- Bis (2-chloroaniline), 4,4'-isopropylidene-dianiline, 4,4'-methylene-bis (3-
Carboxyaniline), 1,3-bis- (3-aminopropyl) tetramethyldisiloxane, 1,3-bis- (2-
Aminoethylaminomethyl) -1,1 ', 3,3'-tetramethyldisiloxane, 1,3-bis- (m-aminophenyl) -1,1', 3,3'-tetramethyldisiloxane, bis (Aminopropyl) polydimethylsiloxane, bis (aminophenyl) polydimethylsiloxane, 1,4-bis (3-aminopropyldimethylsilyl) benzene, bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) diethyl Silane, bis (4-aminophenyl) diphenylsilane, bis (4-aminophenoxy) dimethylsilane, 5,5-methylene-bis- (2-aminophenol), 5,5-oxy-bis- (2-aminophenol ), 5,5-sulfonyl-bis- (2-aminophenol), bis (4-aminophenyl) ethylphosphine oxide, N- [bis- (4-A Nofeniru)] - N-methylamine, N-[bis - (4-aminophenyl)] - N-phenylamine, 5-amino-1-
(4-aminophenyl) -1,3,3-trimethylindane, 3,3'-diamino-diphenylsulfide, 4,4'-
Diamino-diphenyl sulfide, 3,3'-diamino-
Diphenyl sulfone, 4,4'-diamino-diphenyl sulfone, 3,3'-diamino-diphenyl ether, 4,4 '
Diamino-diphenyl ether, 2,2'-bis (trifluoromethyl) -4,4'-diamino-diphenyl ether, 3,3'-bis (trifluoromethyl) -4,4'-diamino-diphenyl ether, 3,3 ', 5,5'-Tetrakis (trifluoromethyl) -4,4'-diamino-diphenyl ether, diaminobenzo-trifluorofluoride,
6-diamino-4-carboxylic benzene, bis {2-[(aminophenoxy) phenyl] hexafluoroisopropyl} benzene, 1,4-bis (p-aminophenoxy) benzene, bis (aminophenoxy) di (trifluoromethyl) ) Benzene, bis (aminophenoxy) tetrakis (trifluoromethyl) benzene, bis [(trifluoromethyl) aminophenoxy] benzene, bis (p-β-methyl-δ-aminopentyl) benzene, p-bis (2-methyl -4-aminopentyl) benzene, p-bis (1,1-dimethyl-5-aminopentyl) benzene, diamino-tetra (trifluoromethyl) benzene, diamino (pentafluoroethyl) benzene, benzidine, 3,3 ′ -Dimethylbenzidine, 3,3 '
-Dimethoxy-benzidine, 2,2'-bis (trifluoromethyl) benzidine, 3,3'-bis (trifluoromethyl) benzidine, 3,3'-dichlorobenzidine, 3,3 '
-Dicarboxybenzidine, 3,3'-diamino-4,4'-
Dicarboxylic benzidine, 3,3'-diamino-biphenyl, 3,4'-diamino-biphenyl, 4,4'-diamino-biphenyl, 3,3'-dimethyl-4,4'-diamino-biphenyl, 4, 4'-bis (p-aminophenoxy)
Biphenyl, bis [(trifluoromethyl) aminophenoxy] biphenyl, 3,3'-diamino-benzophenone, 3,4'-diamino-benzophenone, 4,4'-diamino-benzophenone, 3,3'-bis (trifluoro Methyl) -4,4'-diamino-benzophenone, 3,3'-
Dimethyl-4,4'-diamino-benzophenone, 3,3'-
Dimethoxy-4,4'-diamino-benzophenone, 3,
3'-dichloro-4,4'-diamino-benzophenone,
3,3 "-diamino-p-terphenyl, 4,4" -diamino-p-terphenyl, 4,4-diamino-quarterphenyl, 1,5-diamino-naphthalene, 2,6-diamino-
Naphthalene, 2,4-diamino-toluene, 2,5-diamino-toluene, 2,4-bis (β-amino-t-butyl) toluene and the like can be used, but are not limited thereto.

Q in the group represented by formula (II) of the present invention is In the group represented by, having the group, 1,2-benzoquinonediazide-4-sulfonic acid, 1,2-naphthoquinonediazide-4-sulfonic acid, 1,2-naphthoquinonediazide-5
O-quinonediazide compounds such as sulfonic acid, 2,1-naphthoquinonediazide-4-sulfonic acid, and 2,1-naphthoquinonediazide-5-sulfonic acid are preferred, but not limited thereto.

The polybenzoxazole precursor according to the present invention comprises, for example, an aromatic diaminodihydroxy compound having an X group,
After polycondensation of, for example, a diaminosiloxane having a Z group with, for example, an aromatic dicarboxylic acid chloride or an aromatic dicarboxylic acid or an aromatic dicarboxylic acid ester having a W group or a Y group, a sulfonyl of, for example, O-quinonediazide having a Q group Chloride is dissolved in a solvent such as tetrahydrofuran, diglyme, dimethylsulfoxide, N-methylpyrrolidone, N, N-dimethylacetamide, dimethylformamide and the like, and a base such as triethylamine and pyridine is added as a deacidifying agent, followed by further reaction. Is obtained by The reaction rate of O-quinonediazide to the polybenzoxazole precursor is preferably 2 to 50%, particularly preferably 10 to 20%, based on the number of hydroxyl groups. 2%
Although it can be used even if it is less than 1, solubility in an alkaline aqueous solution becomes too large, so that dissolution of an unexposed portion, that is, film reduction tends to be large. Although it can be used at 50% or more, the hydrophobicity of the polymer increases, and it tends to be insoluble in an aqueous alkaline solution.

The positive photosensitive resin composition of the present invention exhibits excellent adhesion to a substrate such as a silicon oxide film. The conventional positive resist has poor adhesion, and the resist portion to be left during development is peeled off, or cannot be used because etching has a large side etch. Therefore, the wafer was pre-treated with a silylamine derivative, for example, hexamethylene disilazane, chloromethylsilane, or the like, or a silane coupling agent was added to the resin composition to supplement the adhesion, but this was not sufficient. In the present invention, a diaminosiloxane compound represented by the following formula [IV] having a siloxane compound group represented by the formula [V] (Wherein, R ₁ , R ₂ : divalent aliphatic group, aromatic group R ₃ , R ₄ , R ₅ , R ₆ : monovalent aliphatic group, aromatic group k: 1 to 100) 2-20 during the synthesis of the polybenzoxazole precursor
Excellent adhesion is obtained by reacting with mol%, especially 5 to 10 mol%. Although it can be used at less than 2 mol%, the adhesion to the silicon oxide film tends to decrease,
Although it can be used at mol% or more, the film obtained after final curing tends to be brittle.

The positive photosensitive resin composition according to the present invention is exposed to actinic radiation through a mask or irradiated with light, electron beam or ion beam. The exposed or irradiated portion becomes alkali-soluble and is removed with an aqueous alkali solution, and the resulting pattern is converted into a heat-resistant polybenzoxazole by heat treatment.

The positive photosensitive resin composition of the present invention is prepared by dissolving a polybenzoxazole precursor in which the above-mentioned O-quinonediazide is covalently bonded in a solvent, and the solvent includes N-methylpyrrolidone, N, N-dimethylacetamide and the like. Can be used.

The method of using the photosensitive resin composition according to the present invention comprises:
The composition is applied to a suitable support, such as a silicon wafer or a ceramic substrate. The coating method is performed by spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, or the like. Next, after pre-baking at a low temperature of 60 to 100 ° C and drying the coating film,
A desired pattern shape is irradiated with actinic radiation. As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are preferable.

Next, a relief pattern is obtained by dissolving and removing the exposed portion with a developing solution. Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; diethylamine; Secondary amines such as propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, and quaternary ammoniums such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. An aqueous solution of an alkali such as a salt and an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as an alcohol such as methanol or ethanol or a surfactant to the aqueous solution can be suitably used. As a developing method, for example, a method such as spray, paddle, immersion, and ultrasonic wave can be used.

Next, the relief pattern formed by development is rinsed. Distilled water is used as the rinsing liquid. Next, heat treatment is performed to form an oxazole ring, and a final pattern having high heat resistance is obtained.

The photosensitive resin composition according to the present invention is useful not only for semiconductor applications but also as an interlayer insulating film of a multilayer circuit, a cover coat of a flexible copper clad board, a solder resist film, a liquid crystal alignment film, and the like.

 Hereinafter, the present invention will be described specifically with reference to examples.

Example A 4-neck separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube was charged with 1,3-bis (3
-Aminopropyl) tetramethyldisiloxane 3.79 g
(0.015 mol) and 29.30 g of hexafluoro-2,2-bis (2-amino-4-hydroxyphenyl) propane (0.080 m
ol) in 130 ml of dimethylacetamide and 15.82 g of pyridine
(0.200 mol). Next, cyclohexane 40
20.30 g (0.100 mol) of an equimolar mixture of both isophthalic acid chloride and terephthalic acid chloride dissolved in
The mixture was added dropwise at 10 to -15 ° C over 30 minutes, and then stirred at room temperature for 4 hours to complete the reaction. After filtering the reaction mixture, the filtrate was poured into water to precipitate a polymer. The polybenzoxazole precursor (PA) was collected by filtration, sufficiently washed with water, and dried at 80 ° C. under vacuum for one day.

Next, 200 g of this polybenzoxazole precursor (PA) was mixed with 150 ml of tetrahydrofuran and 1.52 g of triethylamine (0.1 g).
015 mol). Next, tetrahydrofuran 10
4.03 g (0.015 mol) of naphthoquinonediazidesulfonic acid chloride dissolved in ml was added dropwise at 0 to 5 ° C. 5 at room temperature
After stirring for an hour, the resulting triethylamine hydrochloride was filtered off, and the filtrate was poured into a mixed solution of water and methanol to precipitate a polymer. The precipitate was collected by filtration, sufficiently washed with a water-methanol solvent, and dried under vacuum at 40 ° C. for one day to obtain a polybenzoxazole precursor (PB) to which naphthoquinonediazide was covalently bonded.

Next, 1.0 part by weight of a polybenzoxazole precursor (PB) having the naphthoquinonediazide covalently bonded thereto was dissolved in 5.0 parts by weight of N-methylpyrrolidone. The obtained solution was applied onto silicon with a spinner, and dried at 80 ° C. for 1 hour with a drier to obtain a film of about 10 μm. This film is provided with a relief printing mask (Toppan Test Chart N)
O.1) Lap, was irradiated with ultraviolet rays of 100 mJ / cm ^2, then 2.38%
Developed with an aqueous solution of tetramethylammonium hydroxide and rinsed well with distilled water.
The pattern up to this point was formed, and it was found that the resolution was high.

Also, no cracks occurred and the residual film ratio was as excellent as 82.0%.

[Effects of the Invention] According to the present invention, a positive photosensitive resin composition having excellent alkali resistance, a wide processing width, and high adhesion to a silicon oxide film can be obtained.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Akira Toko 1-2-2 Uchisaiwai-cho, Chiyoda-ku, Tokyo Sumitomo Bakelite Co., Ltd. Examiner Yoshiko Maeda (56) References JP-A-3-87745 (JP, A (58) Fields surveyed (Int.Cl. ⁶ , DB name) G03F 7/023 G03F 7/075

Claims (3)

(57) [Claims] 1. The following formulas [I], [II], [III], [IV]
Monomers (A), (B),
(C), (D) (Wherein, W: divalent aromatic group) (Wherein, X: tetravalent aromatic group 1: 0-2 m: 1-2 21 + m = 2 (Wherein, Y is a divalent aromatic group) (D) -NH-Z-NH -... [IV] (where Z is a divalent aromatic group or an aliphatic group) is polymerized at the following ratio. (A) 2 to 50 mol%, (B) 2 to 50 mol%, (C) 0 to 48 mol%, (D) 0 to 48 mol% (however, (D) is not 0 mol%) A positive photosensitive resin composition comprising a polybenzoxazole precursor having a degree of polymerization of 2 to 500. 2. The ratio of the total number of m groups in the precursor is The positive photosensitive resin composition according to claim 1, wherein the composition is: 3. A siloxane compound group represented by the following formula [V], wherein the Z group in the precursor is (Wherein, R ₁ , R ₂ : divalent aliphatic group, aromatic group R ₃ , R ₄ , R ₅ , R ₆ : monovalent aliphatic group, aromatic group k: 1 to 100) 3. The positive photosensitive resin composition according to claim 1, wherein the amount of the monomer is 2 to 20 mol%.